EP0300497A1 - Optically active compound, process for producing same and liquid crystal composition containing same - Google Patents
Optically active compound, process for producing same and liquid crystal composition containing same Download PDFInfo
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- EP0300497A1 EP0300497A1 EP88111864A EP88111864A EP0300497A1 EP 0300497 A1 EP0300497 A1 EP 0300497A1 EP 88111864 A EP88111864 A EP 88111864A EP 88111864 A EP88111864 A EP 88111864A EP 0300497 A1 EP0300497 A1 EP 0300497A1
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- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
- C09K19/00—Liquid crystal materials
- C09K19/52—Liquid crystal materials characterised by components which are not liquid crystals, e.g. additives with special physical aspect: solvents, solid particles
- C09K19/58—Dopants or charge transfer agents
- C09K19/586—Optically active dopants; chiral dopants
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C31/00—Saturated compounds having hydroxy or O-metal groups bound to acyclic carbon atoms
- C07C31/34—Halogenated alcohols
- C07C31/38—Halogenated alcohols containing only fluorine as halogen
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C43/00—Ethers; Compounds having groups, groups or groups
- C07C43/02—Ethers
- C07C43/20—Ethers having an ether-oxygen atom bound to a carbon atom of a six-membered aromatic ring
- C07C43/23—Ethers having an ether-oxygen atom bound to a carbon atom of a six-membered aromatic ring containing hydroxy or O-metal groups
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C45/00—Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds
- C07C45/004—Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds by reaction with organometalhalides
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C51/00—Preparation of carboxylic acids or their salts, halides or anhydrides
- C07C51/42—Separation; Purification; Stabilisation; Use of additives
- C07C51/487—Separation; Purification; Stabilisation; Use of additives by treatment giving rise to chemical modification
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C53/00—Saturated compounds having only one carboxyl group bound to an acyclic carbon atom or hydrogen
- C07C53/15—Saturated compounds having only one carboxyl group bound to an acyclic carbon atom or hydrogen containing halogen
- C07C53/19—Acids containing three or more carbon atoms
- C07C53/21—Acids containing three or more carbon atoms containing fluorine
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C65/00—Compounds having carboxyl groups bound to carbon atoms of six—membered aromatic rings and containing any of the groups OH, O—metal, —CHO, keto, ether, groups, groups, or groups
- C07C65/21—Compounds having carboxyl groups bound to carbon atoms of six—membered aromatic rings and containing any of the groups OH, O—metal, —CHO, keto, ether, groups, groups, or groups containing ether groups, groups, groups, or groups
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- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
- C09K19/00—Liquid crystal materials
- C09K19/04—Liquid crystal materials characterised by the chemical structure of the liquid crystal components, e.g. by a specific unit
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- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
- C09K19/00—Liquid crystal materials
- C09K19/04—Liquid crystal materials characterised by the chemical structure of the liquid crystal components, e.g. by a specific unit
- C09K19/0403—Liquid crystal materials characterised by the chemical structure of the liquid crystal components, e.g. by a specific unit the structure containing one or more specific, optionally substituted ring or ring systems
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- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
- C09K19/00—Liquid crystal materials
- C09K19/04—Liquid crystal materials characterised by the chemical structure of the liquid crystal components, e.g. by a specific unit
- C09K19/06—Non-steroidal liquid crystal compounds
- C09K19/08—Non-steroidal liquid crystal compounds containing at least two non-condensed rings
- C09K19/10—Non-steroidal liquid crystal compounds containing at least two non-condensed rings containing at least two benzene rings
- C09K19/12—Non-steroidal liquid crystal compounds containing at least two non-condensed rings containing at least two benzene rings at least two benzene rings directly linked, e.g. biphenyls
- C09K19/126—Compounds containing at least one asymmetric carbon atom
Definitions
- the present invention relates to a novel optically active compound, a process for producing the same and a liquid crystal composition containing the optically active compound.
- optical devices are important as display devices and modulation devices, while the explanation of the individual systems is left to the respective references and omitted.
- Functional materials constituting these optical devices contain an optically active compound or substance as a major component thereof or as a component which is used in a relatively small proportion but constitutes a functionally important part.
- an optically active compound or mesomorphic compound into an optical device material as described above, particularly a liquid crystal material, to control the kind and the temperature range of a liquid crystal phase developed in its liquid crystal state (H. Arnold, Z. Phys. Chem., 226,146 (1964)). It is further expected to add a compound having a large dipole moment into a liquid crystal material driven in response to an electric field to obtain a liquid crystal material having a better electric field-responsive characteristic.
- optically active functional compounds are synthesized through an intermediate which per se is optically active.
- optically active intermediates for synthesizing functional materials necessary for such optical devices characterized by optical activity those compounds are known such as 2-methylbutanol, sec- octyl alcohol, sec-butyl alcohol, p-(2-methylbutyl)benzoic acid chloride, sec-phenethyl alcohol, amino acid derivatives, camphor derivatives and cholesterol derivatives.
- optically active chain hydrocarbon derivatives are difficult to modify their structures and very expensive except for a particular class thereof.
- Amino acid derivatives are relatively cheap and easy to modify their structures, whereas N-hydrogens therein are chemically active and liable to cause hydrogen bonding or other chemical reactions so that the performances of the resultant functional material can be restricted thereby.
- Camphor derivatives and cholesterol derivatives are difficult to modify the structures and the steric hindrance is liable to provide ill effects to the performances of the resultant functional materials.
- a principal object of the present invention is, in view of the above problems, to provide a useful optically active compound which not only is useful as an appropriate optically active intermediate but also provides a high stability and a large spontaneous polarization when synthesized into a mesomorphic compound; a process for producing the same; and a liquid crystal composition containing the same.
- a specific object of the present invention is to provide a compound showing an excellent electric filed response by attaching a group having a large dipole moment to an asymmetric carbon atom.
- Another object of the present invention is to provide a mesomorphic compound capable of readily changing the length of the alkyl chain and therefore capable of controlling a kind of liquid crystal phase to be developed in the liquid crystal state and a temperature range therefor as shown by H. Arnold: Z. Phys. Chem., 226. 146 (1964), and a liquid crystal composition containing at least one of such mesomorphic compounds.
- a further object of the present invention is to provide a compound capable of easily controlling the hydrophobic group and being stably formed into a film when applied to the LB (Langmuir-Blodget) film process for preparing an accumulation of single molecular films.
- the compound represented by the formula (1) not only has functions of controlling a liquid crystal state and improving electric field responsive characteristics as described above, but also is expected to be used for synthesizing various derivatives without losing its optical activity by combining it with other functional intermediates.
- the present invention also provides an optically active 3-trifluoromethylalkanoic acid of the following formula (2):
- R denotes an alkyl group having 1 - 14 carbon atoms and C with denotes an asymmetric carbon atom.
- the present invention further provides an optically active 3-trifluoromethyl-1-alkanol of the following formula (3):
- the compounds represented by the formulas (2) and (3) have an asymmetric carbon atom and a carbonyl group or hydroxyl group connected through a methylene group so that it can be readily converted without losing its optical activity into various derivatives through an ester bond, an ether bond, a urethane bond, a carbonate bond, etc., and therefore are expected to be widely utilized.
- the present invention further provides processes for providing the compounds of the above formulas (2) and (3), wherein trifluoroacetic acid as a starting compound is used to synthesize a racemic mixture of the compound of the formula (2), the racemic mixture is subjected to optical resolution to obtain the optically active compound of the above formula (2), and the compound is further reduced to obtain the optically active compound of the above formula (3).
- optically active compounds represented by the formulas (1), (2) and (3) not only are useful optically active intermediates but also are useful liquid crystal components by themselves. For example, when they are added in a very small amount in a nematic liquid crystal composition for a TN (twisted nematic)-type display device, the occurrence of a fringe pattern (reverse domain) may be effectively prevented to uniformize the display.
- the present invention also provides a liquid crystal composition containing an optically active compound represented by the formula (1), (2) or (3).
- trifluoroacetic acid may be used as a starting material and reacted with an alkylmagnesium bromide or chloride at a low temperature (15°C or below) to obtain a compound of the following formula (4):
- the compound of the formula (4) is reacted with ethyl acetate-triphenylphosphonium bromide to obtain a compound of the following formula (5): Then, the above compound of the formula (5) is successively subjected to hydrogenation and hydrolysis to obtain a racemic mixture of a 3-trifluoromethyl alkanoic acid of the above formula (2).
- the optical resolution of the aikanoic acid or carboxylic acid may be easily effected by forming a diastereomer salt with an optically active base.
- the carboxylic acid may be subjected to optical resolution with a basic optical resolver agent such as (+) or (-)-1-phenylethylamine. whereby an optically active compound of the above formula (2) can be obtained.
- optically active compound of the formula (2) may be further reduced to obtain an optically active compound of the above formula (3).
- optically active compounds of the formulas (2) and (3) according to the present invention can have a wide variety of R by changing the number of carbon atoms in the alkane moiety in the starting alkylmagnesium bromide or chloride but may preferably have an alkyl R of 1 - 14 carbon atoms, particularly 1 - 10 carbon atoms.
- the compound of the formula (1) may be synthesized from an optically active intermediate of the following formula (6): wherein R denotes an alkyl group having 1 - 14 carbon atoms, and Z denotes - - or -CH 2 -.
- reaction may be represented by the following reaction scheme: R and n are the same as defined above.
- optically active compounds of the formulas (1), (2) and (3) may have an alkyl group R having 1 - 14 carbon atoms, preferably 1 - 10 carbon atoms, further preferably 1 - 8 carbon atoms, most preferably 4 - 6 carbon atoms.
- the optically active compounds represented by the formulas (1), (2) and (3) may be used instead of a conventionally used optically active compound such as a hydrocarbon chain derivative, an amino acid derivative, a camphor derivative, or a cholesterol derivative, and may be connected with another intermediate through ester bond, ether bond, urethane bond, carbonate bond, etc., by using a releasable reactive group such as carboxyl group or hydroxyl group.
- a conventionally used optically active compound such as a hydrocarbon chain derivative, an amino acid derivative, a camphor derivative, or a cholesterol derivative
- the optically active compounds are not only useful as an intermediate for producing functional materials constituting optical devices, but also useful as an intermediate for synthesizing various natural optically active compound.
- optically active compounds represented by the formulas (1), (2) and (3) are effectively used for preventing generation of reverse domain in a TN-type cell by adding them into a nematic liquid crystal.
- the optically active compound of the formula (1), (2) or (3) may preferably be used in a proportion of 0.01 - 50 wt. % of the resultant liquid crystal composition.
- the optically active compound may be used to form a chiral nematic liquid crystal composition for use in a phase-transition type liquid crystal device or guest-host type liquid crystal device of the White-Taylor type by adding it into a nematic or chiral nematic liquid crystal.
- the optically active compound of the formula (1), (2) or (3) may preferably be used in a proportion of 0.01 - 80 wt. % of the resultant liquid crystal composition.
- optically active compound of the formula (1), (2) or (3) may be added to a liquid crystal material showing a ferroelectric chiral smectic liquid crystal state by itself in a proportion of 0.01 - 80 wt. % of the liquid crystal composition to form a liquid crystal composition with improved characteristics such as durability.
- the optically active compound of the formula (1), (2) or (3) may be added to a smectic liquid crystal including those shown below at 1) - 5) with structural formulas and phase transition temperatures (0 C), to provide a liquid crystal composition showing a ferroelectric chiral smectic phase.
- the optically active compound of the formula (1), (2) or (3) may be used in a proportion of 0.01 - 80 wt. % of the resultant liquid crystal composition.
- the optically active compound of the formula (1), (2) or (3) is added to provide a chiral smectic liquid crystal composition in the manner as described above, the liquid crystal composition can have a large spontaneous polarization, a shorter response time, and a lower threshold voltage.
- optically active compounds represented by the formulas (1), (2) and (3) which have a trifluoromethyl group providing a large dipole moment directly attached to an asymmetric carbon atom.
- the generation of a reverse domain in a TN-type liquid crystal composition may effectively be prevented, or the electric field responsive characteristic of a chiral nematic liquid crystal or a chiral smectic liquid crystal may be improved, and the liquid crystal state of these liquid crystals may be controlled.
- (+)-1-phe ylethylamine in place of the (-)-1-phenylethylamine in the above operation, (-)-3-trifluoromethyl-1-heptanoic acid can be obtained.
- the sparingly soluble salt showed the following properties:
- a glass substrate provided with an ITO (indium tin oxide) transparent electrode film was coated with a polyimide resin precursor (SP-510, mfd. by Toray K.K.), followed by heating at 300 C for 60 minutes to form a polyimide film. Then, the film was orientation-treated by rubbing. Two glass substrates thus treated were fixed to each other so that their rubbing-treated axes crossed each other at right angles, thereby to form a blank cell with a cell gap of 8 u.m. The cell was filled with a nematic liquid crystal composition (Lixon GR-63, a biphenyl liquid crystal mixture available from Chisso K.K.) to form a TN (twisted nematic)-type cell. When observed through a polarizing microscope, the TN-type cell showed a fringe pattern due to occurrence of reverse domain.
- a nematic liquid crystal composition (Lixon GR-63, a biphenyl liquid crystal mixture available from Chisso K.K.
- a liquid crystal composition was prepared by adding 1 wt. part of the optically active compound obtained by the above Example 2 to 99 wt. parts of the above Lixon GR-63 and used for preparation of a TN cell in the same manner as above.
- the optically active compound of the invention was found to be effective for prevention of reverse domain.
- a TN cell prepared by using a liquid crystal composition prepared by mixing 1 wt. part of the optically active compound obtained in the above Example 1 with 99 wt. parts of p,p -pentylazoxybenzene was observed to provide a nematic phase with remarkably reduced reverse domain as compared with a TN cell prepared without adding the optically active compound.
- a liquid crystal mixture was prepared by adding 5 wt. parts of the optically active compound according to the above Example 2 to 95 wt. parts of a smectic liquid crystal MORA 8 having a structure as shown below.
- the liquid crystal mixture showed an SmC * phase, and showed a spontaneous polarization 1.8 times that of MORA 8 alone and a response time of 25 msec, about 60 % of that of MORA 8 alone, under the voltage application condition of ⁇ 15 V.
- P-(3-trifluoromethylheptyloxy)phenol was prepared through the following steps 1) and 2).
- Step 2 Production of p-(3-trifluoromethylheptyloxy)phenol.
- P-(3-trifluoromethylheptyloxy)benzoic acid was produced through the following steps. 1)-3):
- Step 2 Production of ethyl p-(3-trifluoromethylheptyloxy)benzoate.
- Step 3 Production of p-(3-trifluoromethylheptyloxy)benzoic acid.
- P-(3-trifluoromethylnonyloxy)benzoic acid was produced through the following steps 1) - 3).
- Step 1) Production of 3-trifluoromethylnonyl p-toluenesulfonate.
- Step 2 Production of ethyl p-(3-trifluoromethylnonyloxy)benzoate.
- Step 3 Production of p-(3-trifluoromethylnonyloxy)benzoic acid.
- a liquid crystal mixture was prepared by adding 5 wt. parts of the optically active compound according to the above Example 8 to 95 wt. parts of a smectic liquid crystal MORA 8 having a structure as shown below.
- the liquid crystal mixture showed an SmC * phase, and showed a spontaneous polarization 1.8 times that of MORA 8 alone and a response time of 25 msec, about 60 % of that of MORA 8 alone, under the voltage application condition of ⁇ 15 V.
- a glass substrate provided with an ITO transparent electrode film was coated with a polyimide resin precursor (SP-510, mfd. by Toray K.K.), followed by heating at 300°C for 60 minutes to form a polyimide film. Then, the film was orientation-treated by rubbing. Two glass substrates thus treated were fixed to each other so that their rubbing treated axes crossed each other at right angles, thereby to form a blank cell with a cell gap of 8 um.
- the cell was filled with a nematic liquid crystal composition (Lixon GR-63, a biphenyl liquid crystal mixture available from Chisso K.K.) to form a TN (twisted nematic)-type cell. When observed through a polarizing microscope, the TN-type cell showed a fringe pattern due to occurrence of reverse domain.
- a liquid crystal composition was prepared by adding 1 wt. part of the optically active compound obtained by the above Example 8 to 99 wt. parts of the above Lixon GR-63 and used for preparation of a TN cell in the same manner as above.
- the optically active compound of the invention was found to be effective for prevention of reverse domain.
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Abstract
Description
- The present invention relates to a novel optically active compound, a process for producing the same and a liquid crystal composition containing the optically active compound.
- There have been known various types of optical devices characterized by having optical activities as will be exemplified as follows:
- 1) Those utilizing a cholesteric-nematic phase transition in a liquid crystal state (J.J. Wysoki, A. Adams and W. Haas: Phys. Rev. Lett., 20, 10204 (1968));
- 2) Those utilizing a guest-host effect of the White-Taylor type in a liquid crystal state (D.L. White and G.N. Taylor: J. Appl. Phys., 45. 4718 (1974));
- 3) Those utilizing a ferroelectric liquid crystal effect of a chiral smectic C phase, H phase, F phase, I phase or G phase (N.A. Clark and S.T. Lagerwall: Appl. Phys. Lett., 36, 899 (1980));
- 4) Others including notch filters or band path filters utilizing selective scattering characteristics of a material having a cholesteric phase in the liquid crystal state when fixed in a matrix (F.J. Kahn: Appl. Phys. Lett. 18, 231 (1971)): and circular polarization beam splitters utilizing circular polarization characteristics (S.D. Jacobs, SPIE, 37, 98 (1981)).
- These optical devices are important as display devices and modulation devices, while the explanation of the individual systems is left to the respective references and omitted.
- Functional materials constituting these optical devices contain an optically active compound or substance as a major component thereof or as a component which is used in a relatively small proportion but constitutes a functionally important part. For example, it has been disclosed to add another optically active compound or mesomorphic compound into an optical device material as described above, particularly a liquid crystal material, to control the kind and the temperature range of a liquid crystal phase developed in its liquid crystal state (H. Arnold, Z. Phys. Chem., 226,146 (1964)). It is further expected to add a compound having a large dipole moment into a liquid crystal material driven in response to an electric field to obtain a liquid crystal material having a better electric field-responsive characteristic.
- However, many of the known optically active compounds are not easy to change the length of an introduced group and therefore are not suitable for controlling the liquid crystal state.
- Many of such optically active functional compounds are synthesized through an intermediate which per se is optically active.
- Heretofore, as optically active intermediates for synthesizing functional materials necessary for such optical devices characterized by optical activity, those compounds are known such as 2-methylbutanol, sec- octyl alcohol, sec-butyl alcohol, p-(2-methylbutyl)benzoic acid chloride, sec-phenethyl alcohol, amino acid derivatives, camphor derivatives and cholesterol derivatives.
- However, these intermediates involve respective problems as follows. Thus, optically active chain hydrocarbon derivatives are difficult to modify their structures and very expensive except for a particular class thereof. Amino acid derivatives are relatively cheap and easy to modify their structures, whereas N-hydrogens therein are chemically active and liable to cause hydrogen bonding or other chemical reactions so that the performances of the resultant functional material can be restricted thereby. Camphor derivatives and cholesterol derivatives are difficult to modify the structures and the steric hindrance is liable to provide ill effects to the performances of the resultant functional materials.
- Further, for a class of optical devices utilizing an electric field-responsive optical effect in a liquid crystal state, it has been practiced to introduce a polar group, whereas most of the above mentioned conventional optically active intermediates has a small polarity or have a structure where the polar group cannot be effectively utilized.
- It has been especially known for a ferroelectric liquid crystal that the response speed is proportional to its spontaneous polarization, so that it is desired to increase the spontaneous polarization for achieving a high speed driving. From such a viewpoint, P. Keller et al have shown that it is possible to realize a higher response speed through increase in spontaneous polarization by introducing a chlorine atom so as to be bonded to an asymmetric carbon atom (C.R. Acad. Sc. Paris, 282 C, 639 (1976)). However, the chlorine atom bonded to the asymmetric carbon atom is chemically unstable and has a large atomic radius so that the stability of the liquid crystal phase is lowered. Accordingly, an improvement is still desired.
- A principal object of the present invention is, in view of the above problems, to provide a useful optically active compound which not only is useful as an appropriate optically active intermediate but also provides a high stability and a large spontaneous polarization when synthesized into a mesomorphic compound; a process for producing the same; and a liquid crystal composition containing the same.
- A specific object of the present invention is to provide a compound showing an excellent electric filed response by attaching a group having a large dipole moment to an asymmetric carbon atom.
- Another object of the present invention is to provide a mesomorphic compound capable of readily changing the length of the alkyl chain and therefore capable of controlling a kind of liquid crystal phase to be developed in the liquid crystal state and a temperature range therefor as shown by H. Arnold: Z. Phys. Chem., 226. 146 (1964), and a liquid crystal composition containing at least one of such mesomorphic compounds.
- A further object of the present invention is to provide a compound capable of easily controlling the hydrophobic group and being stably formed into a film when applied to the LB (Langmuir-Blodget) film process for preparing an accumulation of single molecular films.
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- The compound represented by the formula (1) not only has functions of controlling a liquid crystal state and improving electric field responsive characteristics as described above, but also is expected to be used for synthesizing various derivatives without losing its optical activity by combining it with other functional intermediates.
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- The compounds represented by the formulas (2) and (3) have an asymmetric carbon atom and a carbonyl group or hydroxyl group connected through a methylene group so that it can be readily converted without losing its optical activity into various derivatives through an ester bond, an ether bond, a urethane bond, a carbonate bond, etc., and therefore are expected to be widely utilized.
- These optically active compounds represented by the formulas (2) and (3), however, have not been known heretofore. As a result of our intensive study, we have succeeded in synthesis of these compounds and arrived at the present invention.
- Thus, the present invention further provides processes for providing the compounds of the above formulas (2) and (3), wherein trifluoroacetic acid as a starting compound is used to synthesize a racemic mixture of the compound of the formula (2), the racemic mixture is subjected to optical resolution to obtain the optically active compound of the above formula (2), and the compound is further reduced to obtain the optically active compound of the above formula (3).
- The optically active compounds represented by the formulas (1), (2) and (3) not only are useful optically active intermediates but also are useful liquid crystal components by themselves. For example, when they are added in a very small amount in a nematic liquid crystal composition for a TN (twisted nematic)-type display device, the occurrence of a fringe pattern (reverse domain) may be effectively prevented to uniformize the display.
- Thus, the present invention also provides a liquid crystal composition containing an optically active compound represented by the formula (1), (2) or (3).
- The above mentioned and other objects and features of the invention will be better understood upon consideration of the following detailed description concluding with specific examples of production.
- In order to produce optically active compounds of the above formulas (2) and (3) according to the present invention, trifluoroacetic acid may be used as a starting material and reacted with an alkylmagnesium bromide or chloride at a low temperature (15°C or below) to obtain a compound of the following formula (4):
- Next, the compound of the formula (4) is reacted with ethyl acetate-triphenylphosphonium bromide to obtain a compound of the following formula (5):
- The optical resolution of the aikanoic acid or carboxylic acid may be easily effected by forming a diastereomer salt with an optically active base. Thus, the carboxylic acid may be subjected to optical resolution with a basic optical resolver agent such as (+) or (-)-1-phenylethylamine. whereby an optically active compound of the above formula (2) can be obtained.
- Further, the optically active compound of the formula (2) may be further reduced to obtain an optically active compound of the above formula (3).
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- The optically active compounds of the formulas (2) and (3) according to the present invention can have a wide variety of R by changing the number of carbon atoms in the alkane moiety in the starting alkylmagnesium bromide or chloride but may preferably have an alkyl R of 1 - 14 carbon atoms, particularly 1 - 10 carbon atoms.
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- The optically active compounds of the formulas (1), (2) and (3) may have an alkyl group R having 1 - 14 carbon atoms, preferably 1 - 10 carbon atoms, further preferably 1 - 8 carbon atoms, most preferably 4 - 6 carbon atoms.
- As has been briefly mentioned hereinbefore, the optically active compounds represented by the formulas (1), (2) and (3) may be used instead of a conventionally used optically active compound such as a hydrocarbon chain derivative, an amino acid derivative, a camphor derivative, or a cholesterol derivative, and may be connected with another intermediate through ester bond, ether bond, urethane bond, carbonate bond, etc., by using a releasable reactive group such as carboxyl group or hydroxyl group. For this reason, the optically active compounds are not only useful as an intermediate for producing functional materials constituting optical devices, but also useful as an intermediate for synthesizing various natural optically active compound.
- Further, the optically active compounds represented by the formulas (1), (2) and (3) are effectively used for preventing generation of reverse domain in a TN-type cell by adding them into a nematic liquid crystal. In this case, the optically active compound of the formula (1), (2) or (3) may preferably be used in a proportion of 0.01 - 50 wt. % of the resultant liquid crystal composition.
- Further, the optically active compound may be used to form a chiral nematic liquid crystal composition for use in a phase-transition type liquid crystal device or guest-host type liquid crystal device of the White-Taylor type by adding it into a nematic or chiral nematic liquid crystal. In this case, the optically active compound of the formula (1), (2) or (3) may preferably be used in a proportion of 0.01 - 80 wt. % of the resultant liquid crystal composition.
- Further, the optically active compound of the formula (1), (2) or (3) may be added to a liquid crystal material showing a ferroelectric chiral smectic liquid crystal state by itself in a proportion of 0.01 - 80 wt. % of the liquid crystal composition to form a liquid crystal composition with improved characteristics such as durability.
- Furthermore, the optically active compound of the formula (1), (2) or (3) may be added to a smectic liquid crystal including those shown below at 1) - 5) with structural formulas and phase transition temperatures (0 C), to provide a liquid crystal composition showing a ferroelectric chiral smectic phase. In this case, the optically active compound of the formula (1), (2) or (3) may be used in a proportion of 0.01 - 80 wt. % of the resultant liquid crystal composition. When the optically active compound of the formula (1), (2) or (3) is added to provide a chiral smectic liquid crystal composition in the manner as described above, the liquid crystal composition can have a large spontaneous polarization, a shorter response time, and a lower threshold voltage.
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- Herein, the symbols respectively denote the following phases:
- Cryst.: crystal phase
- SmA : smectic A phase
- SmB : smectic B phase
- SmC : smectic C phase
- N : nematic phase
- Iso. : isotropic phase
- As described above, according to the present invention, there are provided optically active compounds represented by the formulas (1), (2) and (3) which have a trifluoromethyl group providing a large dipole moment directly attached to an asymmetric carbon atom.
- Further, by the addition of at least one species of the optically active compounds represented by the formulas (1), (2) and (3), the generation of a reverse domain in a TN-type liquid crystal composition may effectively be prevented, or the electric field responsive characteristic of a chiral nematic liquid crystal or a chiral smectic liquid crystal may be improved, and the liquid crystal state of these liquid crystals may be controlled.
- Hereinafter, the present invention will be more specifically explained with reference to specific examples of production.
-
- In a nitrogen atmosphere, 9.12 g (380 mM) of magnesium into 120 ml of ether, and 49.32 g (360 mM) of butyl bromide dissolved in 30 ml of ether was added thereto, followed by 1.5 hours of heat refluxing. After cooling by standing and with ice, 13.68 g (120 mM) of trifluoroacetic acid dissolved in 30 ml of ether was added. After being stirred for 7 hours under cooling with ice, the system was subjected to hydrolysis with addition of hydrochloric acid, followed by extraction with ether and drying of the resultant ether layer with anhydrous sodium sulfate. The dried product was distilled under normal pressure to obtain 9.46 g of 1,1,1-trifluoro-2-hexanone. Yield: 47 %.
- In a nitrogen atmosphere, 31.47 g (120 mM) of triphenylphosphine was added to 60 ml of benzene, and 23.38 g (140 mM) of ethyl bromoacetate was added under cooling with ice. After 1 hour of stirring at room temperature, the resultant precipitate salt was taken out by filtration and washed with benzene to obtain 48.90 g of ethyl acetate-triphenyl phosphonium bromide. Yield: 95 %.
- In a nitrogen atmosphere, 2.83 g (123 mM) of metallic sodium was dissolved in 50 ml of ethanol, and excessive ethanol was distilled off. Thereto, 340 ml of methylene chloride and 52.71 g (123 mM) of ethyl acetate-triphenylphosphonium bromide prepared in advance were added, and the mixture was stirred for 1 hour. Then, 9.46 g (61.4 mM) of 1,1,1-trifluoro-2-hexanone prepared above and dissolved in 5 ml of methylene chloride was added thereto, and the mixture was stirred for 46 hours. After addition of water, the product was extracted with methylene chloride, dried with anhydrous sodium sulfate and distilled under a reduced pressure to obtain 7.48 g of ethyl 3-trifluoromethyl-2-heptenoate. Yield: 54 %.
- 7.48 g of ethyl 3-trifluoromethyl-2-heptanoate was dissolved in 60 ml of metahnol, and 0.39 g of 5 %- palladium/activated carbon was added thereto, followed by stirring for 4 hours at room temperature and normal pressure in a hydrogen atmosphere in a catalytic hydrogenation apparatus. After the reaction, the 5 %-palladium/activated carbon was filtered out, and the remaining methanol solution was mixed with 60 ml of water and 7 g of potassium hydroxide, followed by 4 hours of heat refluxing, distilling-off of methanol under a reduced pressure, acidification with addition of 6N-hydrochloric acid, and extraction with diethyl ether. The resultant ether solution was dried on sodium sulfate, followed by distilling-off of the solvent and purification by distillation (b.p.: 118.5 - 119.7 C/20 mmHg), whereby 4.6 g of 3-trifluoromethylheptanoic acid was obtained. (yield: 63 %).
- 4.3 g of (±)-3-trifluoromethyl-1-heptanoic acid and 2.7 g of (-)-1-phenylethylamine were dissolved in a twice amount (weight ratio) of hexane under heating, followed by gradual cooling to precipitate a salt. The salt was taken out by filtration and subjected to two times of recrystallization from a twice amount of hexane. The salt was recovered in a yield of 1.6 g and showed a boiling point of 91 - 92 C, and
- By using (+)-1-phe ylethylamine in place of the (-)-1-phenylethylamine in the above operation, (-)-3-trifluoromethyl-1-heptanoic acid can be obtained.
-
-
- In a nitrogen atmosphere, 9.12 g (380 mM) of magnesium into 120 ml of ether, and 59.4 g (360 mM) of hexyl bromide dissolved in 30 ml of ether was added thereto, followed by 1.5 hours of heat refluxing. After cooling by standing and with ice, 13.68 g (120 mM) of trifluoroacetic acid dissolved in 30 ml of ether was added. After being stirred for 7 hours under cooling with ice, the system was subjected to hydrolysis with addition of hydrochloric acid, followed by extraction with ether and drying of the resultant ether layer with anhydrous sodium sulfate. The dried product was distilled under normal pressure to obtain 11.8 g of 1,1,1-trifluoro-2-octanone. Yield: 46 %.
- In a nitrogen atmosphere, 31.47 g (120 mM) of triphenylphosphine was added to 60 ml of benzene, and 23.38 g (140 mM) of ethyl bromoacetate was added under cooling with ice. After 1 hour of stirring at room temperature, the resultant precipitate salt was taken out by fitration and washed with benzene to obtain 48.90 g of ethyl acetate-triphenyl phosphonium bromide. Yield: 95 %.
- In a nitrogen atmosphere, 4.88 g (212 mM) of metallic sodium was dissolved in 80 ml of ethanol, and excessive ethanol was distilled off. Thereto, 544 ml of methylene chloride and 91.0 g (212 mM) of ethyl acetate-triphenylphosphonium bromide prepared in advance were added, and the mixture was stirred for 1 hour. Then, 19.35 g (106 mM) of 1,1,1-trifluoro-2-octanone prepared in advance and dissolved in 10 ml of dry benzene was added thereto, and the mixture was stirred for 48 hours. After addition of water, the product was extracted with methylene chloride, dired with anhydrous sodium sulfate and distilled under a reduced pressure to obtain 13.78 g of ethyl 3-trifluoromethyl-2-nonenoate. Yield: 54.6 %.
- 13.78 g of ethyl 3-trifluoromethyl-2-nonenoate was dissolved in 138 ml of methanol, and 1.38 g of 5 %- palladium/activated carbon was added thereto, followed by stirring for 4 hours at room temperature and normal pressure in a hydrogen atmosphere in a catalytic hydrogenation apparatus. After the reaction, the 5 %-palladium/activated carbon was filtered out, and the remaining methanol solution was mixed with 24 ml, of water and 20 g of potassium hydroxide, followed by 2 hours of heat refluxing, distilling-off of methanol under a reduced pressure, acidification with addition of 6N-hydrochloric acid, and extraction with methylene chloride. The resultant methylene chloride solution was dried on sodium sulfate, followed by distilling-off of the solvent and purification by distillation (b.p.: 118.5 - 119.7°C/20 mmHg), whereby 13.78 g of 3-trifluoromethylnonenoic acid was obtained. (Yield: 51.5 %).
- 9.15 g (40.5 mM) of (:t)-3-trifluoromethyl-1-nonanoic acid and 6.24 g (36.5 mM) of (+)-1-naph- thylethylamine were dissolved in 5 ml of hexane under heating, followed by gradual cooling to precipitate a salt. The salt was taken out by filtration and subjected to two times of recrystallization. The salt was recovered in an amount of 3.00 g (7.55 mM) and the yield was 38.0 % of a half amount of the racemate.
- The sparingly soluble salt showed the following properties:
- [α]589 +3.40° (c 1.03, chloroform)
- Melting point: 103 - 107° C.
- From the salt, 1.32 g (5.84 mM) of 3-trifluoromethyl-1-nonanoic acid was isolated. Yield: 28.1 %. [α]589 -4.75° (c 4.02, chloroform).
- By using (-)-1-naphthyl-1-ethylamine in place of the (+)-1-naphthyl-1-ethylamine in the above operation, (-)-3-trifluoromethyl-1-nonanoic acid can be obtained.
-
- A glass substrate provided with an ITO (indium tin oxide) transparent electrode film was coated with a polyimide resin precursor (SP-510, mfd. by Toray K.K.), followed by heating at 300 C for 60 minutes to form a polyimide film. Then, the film was orientation-treated by rubbing. Two glass substrates thus treated were fixed to each other so that their rubbing-treated axes crossed each other at right angles, thereby to form a blank cell with a cell gap of 8 u.m. The cell was filled with a nematic liquid crystal composition (Lixon GR-63, a biphenyl liquid crystal mixture available from Chisso K.K.) to form a TN (twisted nematic)-type cell. When observed through a polarizing microscope, the TN-type cell showed a fringe pattern due to occurrence of reverse domain.
- A liquid crystal composition was prepared by adding 1 wt. part of the optically active compound obtained by the above Example 2 to 99 wt. parts of the above Lixon GR-63 and used for preparation of a TN cell in the same manner as above. As a result of observation through a polarizing microscope, no reverse domain was observed but a uniform nematic phase was observed in the TN cell. From this fact, the optically active compound of the invention was found to be effective for prevention of reverse domain.
- A TN cell prepared by using a liquid crystal composition prepared by mixing 1 wt. part of the optically active compound obtained in the above Example 1 with 99 wt. parts of p,p -pentylazoxybenzene was observed to provide a nematic phase with remarkably reduced reverse domain as compared with a TN cell prepared without adding the optically active compound.
- A liquid crystal mixture was prepared by adding 5 wt. parts of the optically active compound according to the above Example 2 to 95 wt. parts of a smectic liquid crystal MORA 8 having a structure as shown below. The liquid crystal mixture showed an SmC* phase, and showed a spontaneous polarization 1.8 times that of MORA 8 alone and a response time of 25 msec, about 60 % of that of MORA 8 alone, under the voltage application condition of ±15 V.
-
- 0.48 g of 3-trifluoromethyl-1-heptanol was dissolved in 0.79 g of pyridine, and the solution was cooled with ice, followed by addition of 0.5 g of p-toluenesulfonyl chloride, stirring for 2 hours under cooling with ice and stirring for 2 hours at room temperature. After the reaction, the product was acidified with 2N-hydrochloric acid and extracted with methylene chloride. The resultant methylene chloride solution was washed with water and dried with magnesium sulfate, and the solvent was distilled off, whereby 3-trifluoromethylheptyl p-toluenesulfonate was obtained in an amount of 0.82 g (yield: 92 %) and showed:
- 0.39 g of the above-obtained 3-trifluorometylheptyl p-toluenesulfonate and 0.25 g of hydroquinone were dissolved in 1 ml of butanol. To the solution was added a solution of 0.07 g of sodium hydroxide in 2 ml of butanol, followed by 5 hours of stirring at 130°C for reaction. Then, water and 1 N-hydrochloric acid were added to the reaction solution, followed by extraction with diethyl ether. The ether solution was dried with sodium sulfate, and the solvent was distilled off. The product was then purified by thin layer chromatography with methylene as the developer to obtain 0.17 g (yield: 54 %) of p-(3-trifluoromethylheptyloxy)phenol which showed:
-
- 3-trifluoromethylheptyl p-toluenesulfonate was prepared in the same manner as in Step 1) of Example 8.
- 0.54 g of 3-trifluoromethylheptyl p-toluenesulfonate obtained in Step 1), 0.27 g of ethyl p-hydroxybenzoate and 1 ml of dimethylformamide (DMF) were placed in a round-bottomed flask, and 0.07 g of sodium 60 %-hydride was added thereto together with DMF, followed by 6 hours of stirring at 130 C. After the reaction, DMF was distilled off under a reduced pressure, and water was added, followed by extraction with diethyl ether. The ether solution was dried with sodium sulfate, followed by distilling-off of the solvent to obtain 0.62 g of a crude product. The crude product was then purified by thin layer chromatography with benzene as the developer to obtain 0.22 g of ethyl p-(3-trifluoromethylheptyloxy)benzoate (yield: 42 %).
- 0.082 g of sodium hydroxide was dissolved in 1 ml of water, followed by addition of 3 ml of methanol and 0.22 g of ethyl p-(3-trifluoromethylheptyloxy)benzoate and 3 hours of stirring at 50°C. After the reaction, water was added, methanol was removed by distillation under a reduced pressure, and 6N-hydrochloric acid was added to precipitate a crystal. The crystal was recovered by filtration, washed with water and dried to obtain 0.15 g (yield: 76 %) of p-(3-trifluoromethylheptyloxy)benzoic acid, which showed:
-
- 3.08 mg of 3-trifluoromethyl-1-nonanol was dissolved in 453 mg of pyridine, and the solution was cooled with ice, followed by addition of 276 mg of p-toluenesulfonic chloride, stirring for 2 hours under cooling with ice and stirring overnight at room temperature. After the reaction, the product was acidified with 2N-hydrochloric acid and extracted with diethyl ether. The resultant diethyl ether solution was washed with water and dried with magnesium sulfate, and the solvent was distilled off. The crude product was purified by thin layer chromatography with benzene as the developer to obtain 345 mg (yield: 65 %) of 3-trifluoromethylnonyl p-toluenesulfonate, which showed:
- 345 mg of 3-trifluoromethylnonyl p-toluenesulfonate obtained in Step 1), 166 mg of ethyl p-hydroxybenzoate and 1 ml of dimethylformamdie (DMF) were placed in a round-bottomed flask, and 80 mg of sodium hydride (60 %) was added thereto together with DMF, followed by 6 hours of stirring at 130°C. After the reaction, DMF was distilled off under a reduced pressure, and water was added, followed by extraction with methylene chloride. The methylene chloride solution was dried with magnesium sulfate, followed by distilling-off of the solvent and purification by thin layer chromatography with benzene as the developer to obtain 205 mg of ethyl p-(3-trifluoromethylnonyloxy)benzoate (yield: 60.5 %).
- 72 mg of sodium hydroxide was dissolved in 0.5 ml of water, followed by addition of 0.5 ml of methanol and 205 mg of ethyl p-(3-trifluoromethylnonyloxy)benzoate and 4 hours of stirring at 50' C. After the reaction, water was added, methanol was removed by distillation under a reduced pressure, and 2N-hydrochloric acid was added, followed by extration with diethyl ether. The ether solution was dried with sodium sulfate, and the solvent was distilled off to obtain 146 mg of optically active p-3-trifluoromethyl- nonyloxy)benzoic acid (yield: 77.2 %).
- A liquid crystal mixture was prepared by adding 5 wt. parts of the optically active compound according to the above Example 8 to 95 wt. parts of a smectic liquid crystal MORA 8 having a structure as shown below. The liquid crystal mixture showed an SmC* phase, and showed a spontaneous polarization 1.8 times that of MORA 8 alone and a response time of 25 msec, about 60 % of that of MORA 8 alone, under the voltage application condition of ±15 V.
- A glass substrate provided with an ITO transparent electrode film was coated with a polyimide resin precursor (SP-510, mfd. by Toray K.K.), followed by heating at 300°C for 60 minutes to form a polyimide film. Then, the film was orientation-treated by rubbing. Two glass substrates thus treated were fixed to each other so that their rubbing treated axes crossed each other at right angles, thereby to form a blank cell with a cell gap of 8 um. The cell was filled with a nematic liquid crystal composition (Lixon GR-63, a biphenyl liquid crystal mixture available from Chisso K.K.) to form a TN (twisted nematic)-type cell. When observed through a polarizing microscope, the TN-type cell showed a fringe pattern due to occurrence of reverse domain.
- A liquid crystal composition was prepared by adding 1 wt. part of the optically active compound obtained by the above Example 8 to 99 wt. parts of the above Lixon GR-63 and used for preparation of a TN cell in the same manner as above. As a result of observation through a polarizing microscope, no reverse domain was observed but a uniform nematic phase was observed in TN cell. From this fact, the optically active compound of the invention was found to be effective for prevention of reverse domain.
Claims (8)
Applications Claiming Priority (6)
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JP183485/87 | 1987-07-24 | ||
JP18348687 | 1987-07-24 | ||
JP18348587 | 1987-07-24 | ||
JP183486/87 | 1987-07-24 | ||
JP63037624A JPH0745420B2 (en) | 1987-07-24 | 1988-02-22 | Optically active substance, method for producing the same, and liquid crystal composition containing the same |
JP37624/88 | 1988-02-22 |
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US (2) | US4917817A (en) |
EP (1) | EP0300497B1 (en) |
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DE (1) | DE3888036T2 (en) |
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JPH0764830B2 (en) * | 1987-06-08 | 1995-07-12 | 呉羽化学工業株式会社 | 1,5-Diphenyl-1H-1,2,4-triazol-3-carboxylic acid amide derivative, herbicide containing the derivative and process for producing related compound |
JPH0745420B2 (en) * | 1987-07-24 | 1995-05-17 | キヤノン株式会社 | Optically active substance, method for producing the same, and liquid crystal composition containing the same |
US5424005A (en) * | 1988-02-02 | 1995-06-13 | Showa Shell Sekiyu K.K. | Liquid crystal compounds |
US5204020A (en) * | 1988-02-02 | 1993-04-20 | Showa Shell Sekiyu K.K. | Liquid crystal compounds |
DE3812191A1 (en) * | 1988-04-13 | 1989-10-26 | Merck Patent Gmbh | CHIRAL OR ACHIRREL RING LINKS |
US5250219A (en) * | 1989-05-08 | 1993-10-05 | Canon Kabushiki Kaisha | Mesomorphic compound, liquid crystal composition containing same and liquid crystal device using same |
US5393459A (en) * | 1989-05-11 | 1995-02-28 | Merck Patent Gesellschaft Mit Beschrankter Haftung | Optically active compounds, and a liquid-crystalline phase |
US5139696A (en) * | 1989-05-19 | 1992-08-18 | Cornell Research Foundation, Inc. | Hydrogen-bonded liquid crystal complexes |
US5207946A (en) * | 1989-07-26 | 1993-05-04 | Showa Shell Sekiyu K.K. | Liquid crystal compounds |
JPH0383945A (en) * | 1989-08-28 | 1991-04-09 | Showa Shell Sekiyu Kk | Novel liquid crystal compound and its intermediate |
EP0434297B1 (en) * | 1989-12-18 | 1996-10-16 | Sumitomo Chemical Company Limited | Optically active aromatic compounds, preparation process thereof, and liquid crystal compositions and elements |
JPH03193774A (en) * | 1989-12-22 | 1991-08-23 | Canon Inc | Optically active liquid crystal compound, liquid crystal composition containing same and liquid crystal element using this composition |
JP2822355B2 (en) * | 1989-12-27 | 1998-11-11 | 昭和シェル石油株式会社 | Liquid crystal electro-optic device for driving under three-state ferroelectric conditions |
JP2819332B2 (en) * | 1990-01-29 | 1998-10-30 | キヤノン株式会社 | Liquid crystal compound and liquid crystal composition containing the same |
DE69230386T2 (en) | 1991-02-13 | 2000-06-21 | Canon Kk | Optically active compound, liquid crystalline composition, liquid crystalline device, display apparatus and display method |
JP2002181635A (en) * | 2000-12-15 | 2002-06-26 | Nichiyu Giken Kogyo Co Ltd | Heating temperature confirmation indicator |
Citations (2)
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US4444784A (en) * | 1980-08-05 | 1984-04-24 | Merck & Co., Inc. | Antihypercholesterolemic compounds |
EP0264080A1 (en) * | 1986-10-09 | 1988-04-20 | Daikin Industries, Limited | 5-Fluorouracil derivatives, pharmaceutical composition and use |
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IL34338A (en) * | 1969-06-02 | 1973-04-30 | Rca Corp | Electro-optical devices and compositions containing schiff bases of aromatic aldehydes |
US4613209A (en) * | 1982-03-23 | 1986-09-23 | At&T Bell Laboratories | Smectic liquid crystals |
JPS61254544A (en) * | 1985-05-02 | 1986-11-12 | Asahi Glass Co Ltd | Production of 4,4,4-trifluorovaline compound |
JPS61254537A (en) * | 1985-05-02 | 1986-11-12 | Asahi Glass Co Ltd | Gamma-fluoro-alpha-hydroxycarboxylic acid derivative and production thereof |
JPS61254533A (en) * | 1985-05-02 | 1986-11-12 | Asahi Glass Co Ltd | Production of alpha-substituted-gamma-fluorocarbonyl compound |
DE3534778A1 (en) * | 1985-09-30 | 1987-04-02 | Hoechst Ag | CHIRAL ESTER OF MESOGENIC CARBONIC ACIDS, A METHOD FOR THE PRODUCTION THEREOF AND THEIR USE AS A DOPER IN LIQUID CRYSTAL PHASES |
US4798680A (en) * | 1985-10-18 | 1989-01-17 | Canon Kabushiki Kaisha | Optically active compound, process for producing same and liquid crystal composition containing same |
JPH0699347B2 (en) * | 1986-02-20 | 1994-12-07 | 味の素株式会社 | Optically active CF3 containing compound |
JPH06104827B2 (en) * | 1987-07-31 | 1994-12-21 | キヤノン株式会社 | Ferroelectric liquid crystal element |
JPH0745420B2 (en) * | 1987-07-24 | 1995-05-17 | キヤノン株式会社 | Optically active substance, method for producing the same, and liquid crystal composition containing the same |
DE3812191A1 (en) * | 1988-04-13 | 1989-10-26 | Merck Patent Gmbh | CHIRAL OR ACHIRREL RING LINKS |
-
1988
- 1988-02-22 JP JP63037624A patent/JPH0745420B2/en not_active Expired - Lifetime
- 1988-07-21 US US07/222,426 patent/US4917817A/en not_active Expired - Fee Related
- 1988-07-22 DE DE3888036T patent/DE3888036T2/en not_active Expired - Lifetime
- 1988-07-22 EP EP88111864A patent/EP0300497B1/en not_active Expired - Lifetime
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1991
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Patent Citations (2)
Publication number | Priority date | Publication date | Assignee | Title |
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US4444784A (en) * | 1980-08-05 | 1984-04-24 | Merck & Co., Inc. | Antihypercholesterolemic compounds |
EP0264080A1 (en) * | 1986-10-09 | 1988-04-20 | Daikin Industries, Limited | 5-Fluorouracil derivatives, pharmaceutical composition and use |
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Title |
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CHEMICAL ABSTRACTS, Vol. 102, No. 25, June 24, 1985, Columbus, Ohio, US; K. WEINGES et al. "Nouproteinogenic Amino Acids, II. Synthesis and Determination of the Absolute Configuration of (2S,4S)-(-)-and (2S,4R)-(+)-5,5,5-Trifluoroleucine." page 624, column 1, Abstract-No. 221 160d & Liebigs Ann. Chem. 1985, (1), 90-102 * |
CHEMICAL ABSTRACTS, Vol. 108, No. 23, June 6, 1988, Columbus, Ohio, US; Y. KOBAYASHI et al.: "Preparation of Optically Active Compounds Containing Trifluoromethyl Groups Including Trifluoroleucine", page 633, columns 1,2, Abstract-No. 204 229q; & JP-A-62 192 329 (Kokai Tokkyo Koho) 22-08-1987 * |
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JPH0745420B2 (en) | 1995-05-17 |
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US4917817A (en) | 1990-04-17 |
EP0300497B1 (en) | 1994-03-02 |
DE3888036T2 (en) | 1994-06-23 |
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